CN106635195B - A kind of processing method that biomass refines product altogether - Google Patents
A kind of processing method that biomass refines product altogether Download PDFInfo
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Abstract
The present invention relates to the processing methods that a kind of biomass refines product altogether, including：1) solid biomass, monohydric alcohol and fat compound are added in high-pressure bottle in 200~450 DEG C of refinings altogether, after the completion of reaction, product is separated by solid-liquid separation, collects product liquid；2) product liquid is distilled, collects steaming thing, obtains the A phases based on monohydric alcohol and biomass liquefying product light component；3) extraction and separation are carried out to steaming excess B phases, collects raffinate phase, obtains the oil phase based on biomass liquefying product heavy constituent；4) extraction phase D phases are distilled, collects steaming excess, obtains the light oil phase based on ester type compound, i.e. E phases；5) E phases are contacted with hydrogenation catalyst, makes E phase product hydrogenation deoxidations, to obtain alkane fuel.Method provided by the invention can effectively processing biological refine product altogether, gained alkane fuel can in any proportion be mixed with traditional petroleum based fuels, be a kind of excellent blending component.
Description
Technical field
The invention belongs to the regeneration fields of biomass material, are related to a kind of processing side for refining biomass product altogether
Method.
Background technology
Biomass is can be uniquely converted to the renewable carbon resource of alternative conventional liquid petroleum fuel and other chemicals,
And heat chemistry Efficient Conversion using technology be biomass energy develop and use main approach, therefore biomass high-pressure liquefy
Technology is paid close attention to by many researchers.High-pressure liquefaction refers in solvent medium, and reaction temperature is 200-400 DEG C, reaction pressure
Under conditions of power is 5-25MPa, technique that biomass liquefying is produced into product liquid.It is usually added into catalysis during high-pressure liquefaction
Agent and H2, the reducibility gas such as CO improve liquefied fraction, improve product liquid property.
Current most common high-pressure liquefaction solvent is water, other further include low-carbon alcohols, low-carbon ester, acetone, naphthane, phenol
Or their mixture etc..The characteristics of these solvents is that molecular weight is smaller, to the high-temperature digestion of biomass liquefying macromolecular product
Property it is poor, solid residue is more, and biomass liquefying yield is relatively low, is typically necessary and catalyst is added improves biomass liquefying rate.
For example the patent application of Publication No. CN1952043A proposes biomass liquefied method in water, this method needs to use K2CO3
The equal alkali such as salt or KOH improve the liquefied fraction of biomass for catalyst；The patent application of Publication No. CN101560416A proposes
Liquifying method of the biomass in supercritical methanol, this method are also required to use K2CO3Equal alkali such as salt or KOH carry for catalyst
The liquefied fraction of high biomass.Although salt or alkali is added can improve biomass liquefying rate as catalyst, production is not only increased
Cost also will produce a large amount of waste pollution environment.
Invention content
Present inventor has found that refining (is referred to as biomass to solid biomass altogether in monohydric alcohol with fat compound
Refining altogether), the liquefied fraction of biomass can also be improved.But in the liquid product refined altogether, both product containing biomass liquefying, also fatty
Class compound, is unfavorable for following process.
The present invention relates to the processing methods that a kind of biomass refines product altogether, include the following steps：
1) solid biomass, monohydric alcohol and fat compound are added in high-pressure bottle in 200~450 DEG C of refinings altogether, instead
After the completion of answering, product is separated by solid-liquid separation, collects product liquid；
2) product liquid is distilled, collect steaming thing, obtain be with monohydric alcohol and biomass liquefying product light component
The A phases of main body；
3) extraction and separation are carried out to steaming excess B phases, collects raffinate phase, obtains based on biomass liquefying product heavy constituent
Oil phase, referred to as bio-crude oil phase, i.e. C phases；
4) extraction phase D phases are distilled, collects steaming excess, obtains the light oil phase based on ester type compound, i.e. E
Phase；
5) E phases are contacted with hydrogenation catalyst, makes E phase product hydrogenation deoxidations, to obtain alkane fuel.
In step 1), the solid biomass refer to generated by photosynthesis using big gas and water, soil etc. it is various
The waste and extract that organism and organism generate.The organism includes various plants, animal and microorganism, example
Such as timber, bamboo, algae；The waste include but not limited to agriculture and forestry organic waste material (such as sawdust, stalk, shell etc.),
Human and animal excreta, domestic waste etc.；The extract includes but not limited to lignin, cellulose, hemicellulose, animal egg
It is white etc..
The fat compound refers to being referred mainly to containing the organic compound of at least one C10-C24 Long carbon chains
The aliphatic acid of C10-C24, the fatty alcohol of C10-C24, the fatty aldehyde of C10-C24, the fatty acid amide of C10-C24, C10-C24
The mixture etc. of aliphatic acid C1-C18 alcohol esters, the fatty glyceride of C10-C24 and above compound composition, preferably C10-
C24 fatty glycerides, i.e. animal and plant fat, such as soybean oil, palm oil, lard, butter.
The fat compound can pass through pre-add hydrogen, make part or all of ethylene linkage saturation contained in aliphatic chain, so
Participate in liquefaction reaction again afterwards.
The addition weight of the fat compound is that solid biomass is added 0.1~10 times of weight, preferably 1~8
Times, more preferable 2~6 times.
Solid biomass of the present invention does not include the solid matter rich in fat compound, such as animal tallow.
Described monohydric alcohol refers to the monohydric alcohol of C1-C10, including but not limited to methanol, ethyl alcohol, propyl alcohol, isopropanol etc. or it
Mixture, preferably methanol and ethyl alcohol, more preferable methanol.
The mass ratio of described monohydric alcohol and solid biomass is 1:5‐20:1, preferably 1:1‐10:1, more preferable 1.5:1‐
8:1。
The biological particles size is without restriction, preferably 10~100 mesh, more preferable 30~80 mesh.
The high-pressure bottle type is without restriction, can be reaction kettle or tubular reactor.Such as it is reaction kettle, it can be to reaction
Object is stirred, and mixing speed is unlimited；System pressure is determined by reactant dosage, reactant solvents and reaction temperature, is not necessarily to people
Work is adjusted.Such as it is tubular reactor, reaction pressure is 3~25MPa, preferably 8~20MPa, more preferable 10~18MPa.
The reaction temperature is 200~450 DEG C, preferably 280~360 DEG C.
The reaction time is 3min~6h, preferably 10min~2h.
In step 2), described distillation refers to refining biomass product liquid altogether to distill, with all or part of removing
The light component (i.e. A phases) that the biomass liquefying of monohydric alcohol and boiling point less than 160 DEG C generates.
Described distillation mode includes air-distillation or vacuum distillation, and different vapo(u)rizing temperatures specifically can be used, or
Person takes to distill at the same temperature, also the mode of fractional condensaion can be used to be detached.
In step 3), described extraction and separation refer to carrying out extraction and separation to the steaming excess B phases of step 2) with organic solvent.
Described organic solvent is selected from the low pole or non-polar organic solvent of C5-C20, including but not limited to alkene, alkane, aromatic hydrocarbons
Deng.Described alkane includes C5-C20 linear paraffins, branched paraffin, cycloalkane and its mixture, including but not limited to pentane,
N-hexane, normal heptane, hexamethylene, petroleum ether, kerosene, diesel oil and its component oil etc..Described aromatic hydrocarbons refers to benzene and its derivative, including
But be not limited to benzene,toluene,xylene, trimethylbenzene etc..The preferred C5-C10 alkane of described organic solvent, more preferable petroleum ether.
The addition of described organic solvent is 0.1-10 times, preferably 0.3-5 times, more preferable 0.5-3 times of B phase weight.
Described extraction and separation temperature be room temperature to 150 DEG C, preferably 30 DEG C to 100 DEG C, more preferable 40 DEG C to 80 DEG C.
Described extraction and separation pressure is normal pressure to 1MPa, preferably normal pressure to 0.5MPa, more preferable normal pressure.
Described extraction and separation include the phase separation being added after organic solvent, such as standing sedimentation separation, centrifugation, mistake
Filter separation etc., to obtain organic solvent extraction phase D phases and the bio-crude oil phase based on biomass liquefying product heavy constituent, i.e.,
C phases.
In step 4), the distillation of described extraction phase, refer to the extraction phase containing organic solvent and grease derivative into
Row distillation obtains the light oil phase based on ester type compound to remove the monohydric alcohol and light component of organic solvent and remnants,
That is E phases.
According to the method for the present invention, the described extraction and separation for refining biomass product liquid altogether with organic solvent, can be complete
It carries out, can also be carried out after partial removal monohydric alcohol, the monohydric alcohol not steamed can steam in step 4) after portion's removing monohydric alcohol.
According to the method for the present invention, the described extraction and separation for refining biomass product liquid altogether with organic solvent, can be complete
It carries out, can also be carried out after partial removal light component, the light component not steamed can steam in step 4) after portion's removing light component.
The monohydric alcohol removed in step 2) can be used for the total refining raw material of step 1), and the organic solvent removed in step 4) can be
It is recycled in step 3).
Described hydrogenation catalyst can be non-precious metal catalyst or noble metal catalyst, activearm in step 5)
At least one of oxide or sulfide of the metals such as Pt, Pd, Ru, Co, Mo, Ni, W can be selected from by dividing, by oxide weight
Meter, content are 0.1~50%, preferably 0.5~40%, more preferable the 1~30% of total catalyst weight.Carrier can be selected from activity
Charcoal, Al2O3、SiO2、TiO2One or more of mixture etc..
The hydrogenation catalyst can be prepared according to existing method, such as can refer to CN1229835A, CN1245204A
It is prepared by disclosed method.The hydrogenation deoxidation reaction condition be reaction temperature be 200~450 DEG C, Hydrogen Vapor Pressure be 0.1~
10MPa, standard state hydrogen to oil volume ratio are 100：1~5000：1, oily volume space velocity is 0.1~20h‐1。
Wherein, preferably 220~400 DEG C of described reaction temperature, more preferable 320~380 DEG C.
Described Hydrogen Vapor Pressure preferably 0.5~8MPa, more preferable 2~6MPa.
Described standard state hydrogen to oil volume ratio preferably 300：1~3000：1, more preferable 400：1~2000：1.
Volume space velocity preferably 0.3~10h of described oil‐1, more preferable 0.5~5h‐1。
Above-mentioned steps 5) in, if the active component of used catalyst is the oxide of Co, Mo, Ni, W, need to use CS2
Or H2S carries out presulfurization, it is made to be converted into metal sulfide.
Above-mentioned steps 5) in, if the catalyst used is metal sulfide, sulfur-bearing chemical combination can be added into E phases in advance
Object, such as thiophene, to improve the service life of catalyst.The general weight content for requiring that sulphur is added is 0.05~0.7%.
Above-mentioned steps 5) in, E phases can contact after adding hydrogen with isomerization catalyst and/or Cracking catalyst, keep product different
Structure or molecule become smaller, to produce aviation kerosine.
Biomass high-pressure liquefaction products composition is complicated, and molecular weight is larger, and room temperature is solid-state, and direct hydrogenation deoxidation is relatively more tired
Difficulty is mostly used some model compounds on document and is studied, or biomass high-pressure liquefaction products are dissolved in hexamethylene, tetrahydrochysene
In the organic solvents such as naphthalene, hydrogenation deoxidation is then carried out.The method of the present invention is that solid biomass and grease is total in monohydric alcohol
Refining, while solid biomass liquefies, with monohydric alcohol alcoholysis reaction occurs for grease, obtains the solid biomass that room temperature is liquid
Liquefaction products and grease alcoholysis product.Biomass liquefying product is dissolved in grease alcoholysis product, by being refined altogether biomass
The light oil of product extraction mutually carries out adding hydrogen, it can be achieved that refining biomass the processing of product altogether, production alkane class A fuel A, gained alkane
Fuel can in any proportion be mixed with traditional petroleum based fuels, be a kind of excellent blending component
Solvent need not be additionally added in this process, and biomass liquefying product can be made to have dispersibility well, be conducive to it
Hydrogenation deoxidation, while grease alcoholysis product can also be made to obtain effectively adding hydrogen.
Specific implementation mode
It is further illustrated the present invention below by embodiment, but the present invention is not limited thereto.
Embodiment 1
50g drying Poplar Powders (100 mesh) are added in 500ml autoclaves, and 80g methanol and 80g soybean oils is added, it is close
It is honored as a queen, 300 DEG C is warming up under conditions of low whipping speed 600RPM, keep the temperature 1h, stop heating, Temperature fall to room temperature.Separation
Solid residue, liquid phase weight 188.7g.To liquid phase with 250ml round-bottomed flasks at 80 DEG C air-distillation to no distillate, then
It is distilled at 100 DEG C, 5000Pa, obtains light component (A phases) 14.7g.After liquid in flask is cooled to 50 DEG C, liquid of weighing is
98.7g stirs lower dropwise addition 98.7g hexamethylenes, is stirred 30 minutes after dripping, be then allowed to stand separation.Lower layer is bio-crude oil phase
(C phases), is weighed as 17.3g.The hexamethylene on upper layer is mutually distilled at 100 DEG C, 5000Pa, and resultant product, that is, E phases is weighed as
81.2g, chromatography show that ester type compound accounts for the 90.8% of E phase gross weights.The hydrodesulfurization produced with Chang Ling catalyst plant is urged
(active component is NiO contents 2.9wt%, WO to agent3Content 28wt%, carrier Al2O3) hydrogenation deoxidation is carried out to E phases.Reaction
Condition is：Loaded catalyst is 10mL, in fixed bed reactors, with containing 5%CS2Hexamethylene it is right at 360 DEG C, 4MPa
Presulfiding of catalyst 2h, liquid hourly space velocity (LHSV) 2h‐1, hydrogen-oil ratio is 400 under standard state, makes convert metal oxides by presulfurization
For metal sulfide；Hydrogenation deoxidation carried out to E phases under the conditions of same temperature, pressure, liquid hourly space velocity (LHSV), hydrogen-oil ratio again, in E phases
It is previously added 3000ppm thiophenic sulfurs.After reaction, chromatograph, not oxygen-containing in product, entirely alkane compound.With
Chromatography simulation distillation, the product boiling range of test are as follows：Gasoline fraction section (IBP~180 DEG C) 19.08%, diesel oil distillate section (180
~350 DEG C) 78.96%, kerosene distillate section (140~240 DEG C) 58.89%, distillate section (350~500 DEG C) 1.95%, heavy oil
Fraction section (>500 DEG C) 0%.
Embodiment 2
30g drying willow powder (100 mesh) is added in 500ml autoclaves, and 100g methanol and 80g palm oils is added,
After sealing, it is warming up to 350 DEG C under conditions of low whipping speed 800RPM, keeps the temperature 1.5h, stops heating, Temperature fall to room temperature.
Separating solid residue, liquid phase weight 196.9g.To liquid phase, with 250ml round-bottomed flasks, air-distillation to the nothing at 90 DEG C distillates
Object, then distilled at 100 DEG C, 5000Pa, obtain light component (A phases) 7.3g.After liquid is cooled to room temperature in flask, liquid of weighing
Body is 88.8g, stirs lower dropwise addition 60g petroleum ethers, is stirred 5 minutes after dripping, be then allowed to stand separation.Lower layer is bio-crude oil phase
(C phases), is weighed as 7.5g.The petroleum ether on upper layer is mutually distilled at 100 DEG C, 5000Pa, and resultant product is E phases, is weighed as
81.2g, chromatography show that ester type compound accounts for the 89.8% of E phase gross weights.The 10%Pd/ produced with Xi'an Kai Li chemical companies
C catalyst carries out hydrogenation deoxidation to E phases.Reaction condition is：In autoclave at one with gas flowmeter and counterbalance valve, add
The Pd/C catalyst for entering E phases weight 3%, then in H2It is carried out under the conditions of flow velocity 100mL/min, pressure 2MPa, 300 DEG C of temperature anti-
It answers, reaction time 6h.After reaction, chromatograph, not oxygen-containing in product, entirely alkane compound.With chromatography mould
Quasi- distillation, the product boiling range of test are as follows：Gasoline fraction section (IBP~180 DEG C) 18.21%, diesel oil distillate section (180~350
DEG C) 79.76%, kerosene distillate section (140~240 DEG C) 57.69%, distillate section (350~500 DEG C) 2.03%, heavy oil fraction
Section (>500 DEG C) 0%.
Comparative example 1
50g drying Poplar Powders (100 mesh) are added in 500ml autoclaves, and 80g methanol and 80g soybean oils is added, it is close
It is honored as a queen, 300 DEG C is warming up under conditions of low whipping speed 600RPM, keep the temperature 1h, stop heating, Temperature fall to room temperature.Separation
Solid residue, liquid phase weight 188.7g.Liquid phase is distilled at 100 DEG C, 5000Pa, biomass is obtained and refines product liquid altogether
98.2g, its oxygen content of elemental analysis are 13.0%.(active component is the Hydrobon catalyst produced with Chang Ling catalyst plant
NiO contents 2.9wt%, WO3Content 28wt%, carrier Al2O3) product progress hydrogenation deoxidation is refined biomass altogether.Reaction condition
For：Loaded catalyst is 10mL, in fixed bed reactors, with containing 5%CS2Hexamethylene at 360 DEG C, 4MPa to catalysis
Agent presulfurization 2h, liquid hourly space velocity (LHSV) 2h‐1, hydrogen-oil ratio is 400 under standard state, makes convert metal oxides be gold by presulfurization
Belong to sulfide；Again product liquid is refined biomass altogether under the conditions of same temperature, pressure, liquid hourly space velocity (LHSV), hydrogen-oil ratio to add
Hydrogen deoxidation is previously added 3000ppm thiophenic sulfurs in product.After reaction, elemental analysis shows oxygen content 1.1% in product,
91.5% is reduced compared with reaction raw materials.
Comparative example 2
30g drying willow powder (100 mesh) is added in 500ml autoclaves, and 100g methanol and 80g palm oils is added,
After sealing, it is warming up to 350 DEG C under conditions of low whipping speed 800RPM, keeps the temperature 1.5h, stops heating, Temperature fall to room temperature.
Separating solid residue, liquid phase weight 196.9g.Liquid phase is distilled at 100 DEG C, 5000Pa, biomass is obtained and refines product liquid altogether
88.8g, its oxygen content of elemental analysis are 13.0%.The 10%Pd/C catalyst produced with Xi'an Kai Li chemical companies is to total refining liquid
Body product carries out hydrogenation deoxidation.Reaction condition is：In autoclave at one with gas flowmeter and counterbalance valve, liquid is added
The Pd/C catalyst of products weight 3%, then in H25h is reacted under the conditions of flow velocity 100mL/min, pressure 2MPa, 300 DEG C of temperature.
After reaction, elemental analysis shows oxygen content 0.7% in product, and 94.6% is reduced compared with reaction raw materials.
Comparative example 3
50g drying Poplar Powders (100 mesh), 160g methanol are added in 500ml autoclaves, after sealing, stirred
It is warming up to 300 DEG C under conditions of speed 600RPM, keeps the temperature 1h, stops heating, Temperature fall to room temperature.Isolate solid residue
Afterwards, methanol is distilled out, obtains Poplar Powder liquefaction products (room temperature is solid-state), elemental analysis shows oxygen content 32.1%.Use Chang Ling
(active component is NiO contents 2.9wt%, WO to the Hydrobon catalyst of catalyst plant production3Content 28wt%, carrier are
Al2O3) hydrogenation deoxidation is carried out to Poplar Powder liquefaction products.Reaction condition is：Liquefaction products are dissolved with hexamethylene, and the two ratio is
1：4,20g liquefaction products, 80g hexamethylenes are encased in 500mL reaction kettles, and catalyst 10g, CS is then added2Addition
For 1.1g, Hydrogen Vapor Pressure 50bar.After sealing reaction kettle, to the pre- sulphur of catalyst at low whipping speed 500RPM, 320 DEG C of temperature
Change 2h, makes convert metal oxides be metal sulfide by presulfurization；Liquefaction products are carried out under the conditions of 360 DEG C again to add hydrogen
Deoxidation 2h.After reaction, chromatograph reduces 74.4% oxygen-containing 8.2% in product compared with reaction raw materials.
Comparative example 4
30g drying willow powder (100 mesh), 180g methanol are added in 500ml autoclaves, after sealing, low whipping speed
It is warming up to 350 DEG C under conditions of 800RPM, keeps the temperature 1.5h, stops heating, Temperature fall to room temperature.After isolating solid residue,
Methanol is distilled out, obtains willow powder liquefaction products (room temperature is solid-state), elemental analysis shows oxygen content 30.8%.It is triumphant with Xi'an
The 10%Pd/C catalyst of vertical chemical company's production is to carrying out hydrogenation deoxidation.Reaction condition is：20g liquid is dissolved with 80g naphthanes
Change product, is then added in an autoclave with gas flowmeter and counterbalance valve, adds the Pd/C of raw material weight 3%
Catalyst, then in H2It is reacted under the conditions of flow velocity 100mL/min, pressure 2MPa, 300 DEG C of temperature, reaction time 6h.Instead
After answering, chromatograph reduces 70.1% oxygen-containing 9.2% in product compared with reaction raw materials.
Claims (16)
1. the processing method that a kind of biomass refines product altogether, includes the following steps：
1) solid biomass, monohydric alcohol and fat compound are added in high-pressure bottle in 200~450 DEG C of refinings altogether, have been reacted
Cheng Hou is separated by solid-liquid separation product, collects product liquid；
2) product liquid is distilled, collects steaming thing, obtains based on monohydric alcohol and biomass liquefying product light component
A phases；
3) extraction and separation are carried out to steaming excess B phases, collects raffinate phase, obtains the oil based on biomass liquefying product heavy constituent
Phase, i.e. C phases；
4) extraction phase D phases are distilled, collects steaming excess, obtains the light oil phase based on ester type compound, i.e. E phases；
5) E phases are contacted with hydrogenation catalyst, makes E phase product hydrogenation deoxidations, to obtain alkane fuel.
2. according to the method for claim 1, wherein the solid biomass includes that various organisms and organism generate
Waste and extract.
3. according to the method for claim 1, wherein the fat compound refers to containing at least one C10-C24
The organic compound of Long carbon chain.
4. according to the method for claim 3, wherein the fat compound is selected from aliphatic acid, the C10- of C10-C24
The fatty alcohol of C24, the fatty aldehyde of C10-C24, the fatty acid amide of C10-C24, C10-C24 aliphatic acid C1-C18 alcohol esters and
The mixture of above compound composition.
5. according to the method for claim 4, wherein the fat compound is selected from the fatty acid glycerine of C10-C24
Ester.
6. according to the method for claim 1, wherein the addition weight of the fat compound is solid biomass weight
0.1~10 times of amount.
7. according to the method for claim 1, wherein described monohydric alcohol is selected from the monohydric alcohol of C1-C10.
8. according to the method for claim 1, wherein described monohydric alcohol is selected from methanol and/or ethyl alcohol.
9. according to the method for claim 1, wherein the mass ratio of described monohydric alcohol and solid biomass is 1:5‐20:
1。
10. according to the method for claim 1, wherein the high-pressure bottle is reaction kettle or tubular reactor, reaction pressure
Power is 3~25MPa.
11. according to the method for claim 1, wherein the reaction temperature is 280~360 DEG C.
12. according to the method for claim 1, wherein in step 3), the organic solvent that described extraction and separation use is selected from
The low pole or non-polar organic solvent of C5-C20.
13. according to the method for claim 12, wherein described organic solvent be selected from pentane, n-hexane, normal heptane,
It is one or more in hexamethylene, petroleum ether, kerosene, diesel oil and its component oil, benzene,toluene,xylene, trimethylbenzene.
14. according to the method for claim 12, wherein the addition of described organic solvent is the 0.1-10 of B phase weight
Times.
15. according to the method for claim 1, wherein the active component of described hydrogenation catalyst be selected from Pt, Pd, Ru, Co,
One or more of Mo, Ni, W, on the basis of overall catalyst weight, weight content of the active component in terms of oxide be 0.1~
50%, catalyst carrier is selected from activated carbon, Al2O3、SiO2、TiO2In one or more mixtures.
16. according to the method for claim 1, wherein described hydrogenation deoxidation reaction condition be reaction temperature be 150~
400 DEG C, Hydrogen Vapor Pressure is 0.1~10MPa, and reaction carries out in intermittently or serially flow reactor；In batch reactor, urge
Agent dosage is the 0.1~10% of weight of oil, and the reaction time is 0.5~15h；In continuous flow reactor, standard state hydrogen
Oil volume ratio is 100：1~2000：1, oily volume space velocity is 0.01~5h‐1。
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| "麦秆超临界醇解液化产物的萃取分离及分析";杨华美等;《安徽农业科学》;20121231;第40卷(第5期);第2938-2941页 * |
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